CN105008378A - Reaction catalyst for cross coupling and method for manufacturing aromatic compound - Google Patents

Reaction catalyst for cross coupling and method for manufacturing aromatic compound Download PDF

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CN105008378A
CN105008378A CN201480005612.8A CN201480005612A CN105008378A CN 105008378 A CN105008378 A CN 105008378A CN 201480005612 A CN201480005612 A CN 201480005612A CN 105008378 A CN105008378 A CN 105008378A
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隈元信满
铃木健太
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Hokko Chemical Industry Co Ltd
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Abstract

The purpose of the present invention is to provide new organic phosphorus-based ligands that can efficiently perform a cross coupling reaction to obtain a target substance with high yield; and also to provide a manufacturing method that can finely adjust the steric properties and electrical properties, and can perform a cross coupling reaction with high-efficiency using these ligands. A phosphine compound expressed by general formula (1) is provided as resolution means. In the formula, R<1> and R<2> each independently represent a secondary alkyl group, tertiary alkyl group, or cycloalkyl group; and R<3> and R<4> each independently represent a hydrogen, aliphatic group, heteroaliphatic group, aromatic group, alicyclic group, or heterocyclic group. Further R<3> and R<4> do not contain a phosphorus atom, and R<3> and R<4> are not both simultaneously hydrogen.

Description

The manufacture method of cross-coupling catalysts and aromatics
Technical field
The present invention relates to novel organophosphorus class coordination compound catalyzer, Novel phosphine ligand, the manufacture method of above-mentioned substance and above-mentioned substance in organic synthesis as the application of catalyzer, particularly relate to the application in the linked reaction halogenide and Pseudohalides with aryl, heteroaryl or vinyl used as initial substance.
Background technology
Linked reaction is the important reaction for generating C-C and carbon-heteroatom bond.By the compound that linked reaction manufactures, such as, the hole mobile material that aromatic amines compound uses as organic electroluminescent device etc., luminescent material are useful, thus propose various structures.In addition, the aromatics utilizing Suzuki-Pu, palace reaction to manufacture is widely used as the intermediate of medicine, agricultural chemicals, pigment.
As the manufacture method of aromatic amines compound, known just have since ancient times under the existence of palladium complex and triaryl phosphine, makes to have the method (with reference to patent documentation 1) that the aromatics of halogen atom and primary amine or secondary amine carry out cross-coupling reaction.But, their reactivity is low, the yield becoming the aromatic amines compound of target is insufficient, carried out large quantifier elimination up to now, its result proposes the catalyzer (with reference to patent documentation 2) of di-t-butyl (4-dimethylaminophenyl) phosphine of the rich and three-dimensional volume with electronics etc.In addition, there was reported Suzuki-Pu, the palace reaction (with reference to non-patent literature 1,2) employing various Phosphine ligands.
Prior art document
Patent documentation
Patent documentation 1 United States Patent (USP) No. 5576460 specification sheets
Patent documentation 2 Japanese Unexamined Patent Publication 2009-298773 publication
Non-patent literature
Non-patent literature 1 The Journal of Organic Chemistry, 2007, the 72nd volume, 5104-5112 page
Non-patent literature 2 Chemical reviews nineteen ninety-five, the 95th volume, 2457-2483 page
Summary of the invention
In recent years, as organic electronic material, doctor's pesticide intermediate, the compound in a large number with massive structure has been synthesized.In addition, cheapness is sought similarly and the reaction undertaken by the matrix with chlorine atom that reactivity is low.Such as, the cross-coupling shown in patent documentation 2 has bulky substituent, when the reactivity of matrix is low, there is the low such problem of yield becoming the aromatic amines compound of target.This is the common common problem of cross-coupling reaction.Secondly, the stereospecificity of applicable reactive system and the fine setting of characteristic electron is needed to carry out and the higher catalyzer of activity.
Therefore, technical problem to be solved by this invention is to provide efficiently can carry out cross-coupling reaction and novel organophosphorus class part and the organic phosphates coordination compound catalyzer that can obtain target compound with high yield, the fine setting can carrying out stereospecificity and characteristic electron is provided further, and the manufacture method by using above-mentioned substance can carry out cross-coupling reaction with high yield.
Present inventor conducts in-depth research repeatedly in order to solve the problem, and found that the R by changing following general formula (1) 1, R 2, R 3and R 4, when use have can carry out the part of the structure of the fine setting of stereospecificity and characteristic electron time, cross-coupling reaction can be carried out with high yield.
That is, the present invention is as described below concludes.
(1) phosphine compound, is characterized in that, is represented by following general formula (1),
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
(2) phosphine compound Gen Ju (1), is characterized in that, R in general formula (1) 1with R 2be the tertiary butyl.
(3) phosphine compound Gen Ju (2), is characterized in that, is represented by following formula (2).
(4) phosphine compound Gen Ju (2), is characterized in that, is represented by following formula (3).
(5) a coordination compound catalyzer, is characterized in that, the phosphine compound that following general formula (1) represents be coordinated in be selected from the periodic table of elements the 8th race, the 9th race, the 10th race and the 11st race transition metal and formed,
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
(6) according to (5) described coordination compound catalyzer, it is characterized in that, transition metal is selected from Pd, Ni, Pt, Rh, Ir, Ru, Co, Fe, Cu and Au.
(7) according to (6) described coordination compound, it is characterized in that, represented by following formula (4),
PdCl 2(tBu 2P-CH 2-CH＝CH-CH 3) 2(4)
In formula, tBu represents the tertiary butyl.
(8) according to (6) described coordination compound, it is characterized in that, represented by following formula (5),
PdCl 2(tBu 2P-CH 2-CH＝C(CH 3) 2) 2(5)
(9) mono-Zhong phosphonium salt compounds, is characterized in that, are represented by following general formula (6),
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, Y -represent B -f 4or B -ph 4.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
(10) according to (9) Suo Shu phosphonium salt compound, it is characterized in that, R in formula (6) 1and R 2for the tertiary butyl.
(11) a kind of manufacture method of aromatics, it is characterized in that, the phosphine compound that formula (1) is represented and/or formula (6) Biao Shi phosphonium salt compound be selected from the 8th race of the periodic table of elements, the 9th race, the 10th race and the 11st race transistion metal compound add in reaction solution and generate coordination compound, using this coordination compound as catalyzer or as catalyst system at least partially, and use this catalyzer or catalyst system
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4be asynchronously hydrogen atom,
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, Y -represent B -f 4or B -ph 4.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
(12) a kind of manufacture method of aromatics, it is characterized in that, the phosphine compound that following general formula (1) represents be coordinated in be selected from the periodic table of elements the 8th race, the 9th race, the 10th race and the 11st race transition metal thus form coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
(13) a kind of manufacture method of aromatic amines compound, it is characterized in that, comprise following content: the phosphine compound that formula (1) is represented and/or formula (6) Biao Shi phosphonium salt compound be selected from the 8th race of the periodic table of elements, the 9th race, the 10th race and the 11st race transistion metal compound add in reaction solution and generate coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system, make to have the aromatics of halogen atom and/or reactive behavior base and primary amine and/or secondary amine to react
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, Y -represent B -f 4or B -ph 4.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
(14) a kind of manufacture method of aromatic amines compound, it is characterized in that, comprise following content: the phosphine compound that following general formula (1) represents be coordinated in be selected from the periodic table of elements the 8th race, the 9th race, the 10th race and the 11st race transition metal thus form coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system, make to have the aromatics of halogen atom and/or reactive behavior base and primary amine and/or secondary amine to react
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
(15) a kind of manufacture method of aromatics, it is characterized in that, comprise following content: the phosphine compound that formula (1) is represented and/or formula (6) Biao Shi phosphonium salt compound be selected from the 8th race of the periodic table of elements, the 9th race, the 10th race and the 11st race transistion metal compound add in reaction solution and generate coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system, the aromatics and the boron compound that make to have halogen atom and/or reactive behavior base react
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4be asynchronously hydrogen atom,
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, Y -represent B -f 4or B -ph 4.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
(16) a kind of manufacture method of aromatics, it is characterized in that, comprise following content: the phosphine compound that following general formula (1) represents be coordinated in be selected from the periodic table of elements the 8th race, the 9th race, the 10th race and the 11st race transition metal thus form coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system, the aromatics and the boron compound that make to have halogen atom and/or reactive behavior base react
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
When using the catalyzer using organo phosphorous compounds as part of the present invention, efficiently cross-coupling reaction can be carried out.In addition, the stereospecificity of applicable reactive system and the fine setting of characteristic electron can be carried out.Therefore, by implementing manufacture method of the present invention, aromatics can be manufactured with high yield, and the aromatics of biphenol compound, aromatic amine etc. can be obtained with high yield.In addition, metal complexes of the present invention is stablized, and also easily processes.As known from the above, manufacture method of the present invention is useful in the manufacture of organic electronic material, doctor's pesticide intermediate, is industrially worth high.
Embodiment
(phosphine compound)
In the phosphine compound that general formula of the present invention (1) represents, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another.During for secondary alkyl, for being selected from the alkyl of C3 ~ C18, more favourable then preferred C3 ~ C6, in addition, during for tertiary alkyl, for being selected from the alkyl of C4 ~ C18, more favourable then preferred C4 ~ C8.Specifically, preferred sec.-propyl, sec-butyl, the tertiary butyl.The most preferably tertiary butyl.Cycloalkyl can be any one in monocyclic or polycycle cycloalkyl, such as, also can be adamantyl or norcamphyl.The cycloalkyl of preferred C3 ~ C8, more preferably cyclohexyl.
R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.But, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
As fatty group, be the alkynyl of the alkyl of C1 ~ C18, the alkenyl of C2 ~ C18 or C2 ~ C18, above-mentioned group also can be straight-chain or branched.Assorted fatty group is the heteroatoms comprising at least 1 Sauerstoffatom, nitrogen-atoms etc. in alkyl, alkenyl or alkynyl, and above-mentioned group can be straight-chain and also can be branched.Ester ring type base comprises the cycloalkyl of C3 ~ C18, the cycloalkenyl group of C5 ~ C18, can be monocycle and also can be polycycle class.Aromatic series base comprises monocycle class and many lopps.Hetero ring type base is included in ester ring type base has at least 1 heteroatomic group in this ring structure, and has at least 1 heteroatomic group in this ring structure in aromatic series base.
Above-mentioned substituting group can be replaced by other substituting group further, and such as, fatty group can be replaced by aromatic series base thus form aralkyl, or contrary aromatic series base can be replaced by fatty group thus form alkylaryl.
As most preferred R 1with R 2combination, be the tertiary butyl, or be cyclohexyl, or the tertiary butyl and cyclohexyl, as R 3with R 4combination, be methyl and hydrogen atom, or be methyl.Specifically, di-t-butyl crot(on)yl phosphine, di-t-butyl prenyl phosphine, dicyclohexyl crot(on)yl phosphine, dicyclohexyl prenyl phosphine, tert-butylcyclohexyl crot(on)yl phosphine, tert-butylcyclohexyl prenyl phosphine is referred to.
For having for the di-t-butyl allyl group phosphine, di-t-butyl normal-butyl phosphine etc. of similar structures with phosphine compound of the present invention, as viewed in comparative example 2 described later, comparative example 9, when can find to contrast with phosphine compound of the present invention, in cross-coupling reaction, yield obviously reduces.On the other hand, in the compound of general formula of the present invention (1), work as R 3with R 4be combined as methyl and hydrogen atom or R 3, R 4when being methyl, the yield of cross-coupling reaction significantly improves, and also the known effect produced by the present invention is special and excellent thus.
In addition, R is changed according to reactive system 1, R 2and/or R 3, R 4group, the fine setting of its stereospecificity and characteristic electron can be carried out accordingly.Such as, in the reaction of embodiment 10, R 3with R 4the di-t-butyl crot(on)yl phosphine being combined as methyl and hydrogen atom effective, in the reaction of embodiment 12, R 3, R 4the di-t-butyl prenyl phosphine being methyl is effective.
The present invention is following phosphine compound: especially such as formula (1) compound shown in, as internal alkene (R 3, R 4in at least one be group beyond hydrogen atom) instead of terminal olefin (i.e. R 3, R 4be hydrogen atom), by changing the electron density of alkene, cross-coupling reaction can be carried out more with high yield.
As such phosphine compound of the present invention, following phosphine compound can be enumerated, but be not limited to illustrative compound.
Di-isopropyl crot(on)yl phosphine, di-isopropyl prenyl phosphine, di-isopropyl-pentenyl phosphine, di-isopropyl-5-methyl-2-hexenyl phosphine, di-isopropyl-3-cyclohexyl-2-propenyl phosphine, the fluoro-crotyl phosphine of di-isopropyl-4-, di-isopropyl-4-methoxyl group-crotyl phosphine, di-isopropyl-4-dimethylamino-crotyl phosphine, di-isopropyl-2,4-hexadienyl phosphine, own-4-alkynes-1-base the phosphine of di-isopropyl-2-, di-isopropyl cinnamyl phosphine, di-isopropyl-3-(4-fluorophenyl) propenyl phosphine, di-isopropyl-3-(4-p-methoxy-phenyl) propenyl phosphine, di-isopropyl-3-(4-dimethylaminophenyl) propenyl phosphine, di-isopropyl-3-(2-furyl) propenyl phosphine, di-isopropyl-3-(2-pyridyl) propenyl phosphine, di-isopropyl-3-(2-thienyl) propenyl phosphine, dicyclohexyl crot(on)yl phosphine, dicyclohexyl prenyl phosphine, dicyclohexyl-pentenyl phosphine, dicyclohexyl-5-methyl-2-hexenyl phosphine, dicyclohexyl-3-cyclohexyl-2-propenyl phosphine, the fluoro-crotyl phosphine of dicyclohexyl-4-, dicyclohexyl-4-methoxyl group-crotyl phosphine, dicyclohexyl-4-dimethylamino-crotyl phosphine, dicyclohexyl-2,4-hexadienyl phosphine, own-4-alkynes-1-base the phosphine of dicyclohexyl-2-, dicyclohexyl cinnamyl phosphine, dicyclohexyl-3-(4-fluorophenyl) propenyl phosphine, dicyclohexyl-3-(4-p-methoxy-phenyl) propenyl phosphine, dicyclohexyl-3-(4-dimethylaminophenyl) propenyl phosphine, dicyclohexyl-3-(2-furyl) propenyl phosphine, dicyclohexyl-3-(2-pyridyl) propenyl phosphine, dicyclohexyl-3-(2-thienyl) propenyl phosphine, di-t-butyl crot(on)yl phosphine, di-t-butyl prenyl phosphine, di-t-butyl-pentenyl phosphine, di-t-butyl-5-methyl-2-hexenyl phosphine, di-t-butyl-3-cyclohexyl-2-propenyl phosphine, the fluoro-crotyl phosphine of di-t-butyl-4-, di-t-butyl-4-methoxyl group-crotyl phosphine, di-t-butyl-4-dimethylamino-crotyl phosphine, di-t-butyl-2,4-hexadienyl phosphine, own-4-alkynes-1-base the phosphine of di-t-butyl-2-, di-t-butyl cinnamyl phosphine, di-t-butyl-3-(4-fluorophenyl) propenyl phosphine, di-t-butyl-3-(4-p-methoxy-phenyl) propenyl phosphine, di-t-butyl-3-(4-dimethylaminophenyl) propenyl phosphine, di-t-butyl-3-(2-furyl) propenyl phosphine, di-t-butyl-3-(2-pyridyl) propenyl phosphine, di-t-butyl-3-(2-thienyl) propenyl phosphine.
(synthesis of phosphine compound)
Synthesize by following reaction as the phosphine compound shown in general formula of the present invention (1): in the dialkyl group phosphonium chloride shown in general formula (7), make the Grignard reagent shown in general formula (8) react using copper compound as catalyzer.In general formula (7), R 1and R 2represent the secondary alkyl of C3 ~ C18, the tertiary alkyl of C4 ~ C18 or the cycloalkyl of C3 ~ C18 independently of one another, more favourable is then secondary alkyl or the tertiary alkyl of C4 ~ C8, the cycloalkyl of C3 ~ C8 of C3 ~ C6.As the concrete example of secondary alkyl, tertiary alkyl, can be sec.-propyl, sec-butyl, the tertiary butyl.The most preferably tertiary butyl.Cycloalkyl also can be the such polycycle base of monocyclic or adamantyl or norcamphyl.Preferred cycloalkyl is cyclohexyl.
In the Grignard reagent shown in (8), R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another.In addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.As fatty group, be alkyl, alkenyl or alkynyl, above-mentioned group also can be straight-chain or branched.Assorted fatty group is in alkyl, alkenyl or alkynyl, and in its skeleton or as bonded atom, additionally comprise at least 1 heteroatoms, such as, have the group of Sauerstoffatom or nitrogen-atoms, above-mentioned group can be straight-chain and also can be branched.Ester ring type base comprises cycloalkyl, cycloalkenyl group, can be monocycle and also can be polycycle class.Aromatic series base comprises monocycle class and many lopps.Hetero ring type base is included in ester ring type base has at least 1 heteroatomic group in this ring structure, and has at least 1 heteroatomic group in this ring structure in aromatic series base.
Above-mentioned substituting group can be replaced by other substituting group further, and such as, fatty group can be replaced by aromatic series base thus form aralkyl, or contrary aromatic series base can be replaced by fatty group thus form alkylaryl.
As most preferred R 3and R 4be combined as methyl and hydrogen atom.
In addition, X represents chlorine atom, bromine atoms or atomic iodine.
Even if reaction solvent is separately the ether solvent of tetrahydrofuran (THF), diethyl ether etc., or with the mixing system of the fragrant same clan of benzene, toluene etc. or the varsol of hexane, heptane etc., also can obtain same result.
Such as, the di-t-butyl crot(on)yl phosphine shown in general formula (2) is obtain by being added drop-wise in di-t-butylchlorophosphine under copper catalyst exists by the Grignard reagent of crotyl chloride or the chloro-1-butylene of 3-.
Relative to the dialkyl group halogenation phosphine of general formula (7), the usage quantity of copper compound is comparatively applicable from 0.1 % by mole ~ 10 % by mole.Particularly preferably the usage quantity of copper compound is 0.5 % by mole ~ 3 % by mole relative to the dialkyl group halogenation phosphine of general formula (7).In addition, the kind of this copper compound can use any one in Inorganic Copper and organic copper, particularly preferably copper halide or cupric acetylacetonate (II).
In addition, relative to the dialkyl group halogenation phosphine of general formula (7), the usage quantity of the Grignard reagent of the general formula (8) that the synthetic method of phosphine compound of the present invention uses is 0.5 equivalent ~ 5 equivalent.Relative to the dialkyl group halogenation phosphine of general formula (7), the usage quantity of the Grignard reagent of preferred general formula (8) is 0.9 equivalent ~ 1.5 equivalent.
As long as the treatment process after having reacted is according to the synthesis method of common tertiary phosphine compounds class of being undertaken by Grignard reagent.Namely, in order to remove the inorganic salt of secondary raw magnesium halide etc., mix the dilute acidic aqueous solutions of the water or dilute sulphuric acid etc. only having dissolved inorganic salt in reactive system after, separatory removing water layer, and residual organic layer is heated up in a steamer used solvent under normal pressure or decompression, the tertiary phosphine of the general formula (1) becoming target can be obtained accordingly.
In addition, when being isomerizated into as problem, as other manufacture method, such as, the reaction etc. of the reaction of halogenation phosphine and organolithium reagent, the reaction of dialkyl phosphine and alkene, the reaction of dialkyl phosphine and alkenyl halogen, the phosphide prepared from halogenation phosphine and metallic lithium etc. and alkenyl halogen can be enumerated.But, be not limited to aforesaid method.
(being coordinated in phosphine compound to be formed) organic phosphates coordination compound catalyzer
A mode of the present invention is as follows, and described phosphine compound, for being coordinated in transition metal, is particularly selected from the 8th race of periodictable, the 9th race, the transition metal of the 10th race and the 11st race and the coordination compound formed.It is favourable that transition metal is selected from Pd, Ni, Pt, Rh, Ir, Ru, Co, Fe, Cu and Au, and this metal is that Pd or Ni is more favourable, and this metal is that Pd is the most favourable.As such coordination compound of the present invention, can following substances be enumerated, but be not limited to illustrative compound.
Two (di-isopropyl crot(on)yl phosphine) palladium, two (di-isopropyl prenyl phosphine) palladium, two (two (di-isopropyl-pentenyl phosphine) palladium, two (di-isopropyl-5-methyl-2-hexenyl phosphine) palladium, two (di-isopropyl-3-cyclohexyl-2-propenyl phosphine) palladium, two (the fluoro-crotyl phosphine of di-isopropyl-4-) palladium, two (di-isopropyl-4-methoxyl group-crotyl phosphine) palladium, two (di-isopropyl-4-dimethylamino-crotyl phosphine) palladium, two (di-isopropyl-2,4-hexadienyl phosphine) palladium, two (own-4-alkynes-1-base phosphine of di-isopropyl-2-) palladium, two (di-isopropyl cinnamyl phosphine) palladium, two (di-isopropyl-3-(4-fluorophenyl) propenyl phosphine) palladium, two (di-isopropyl-3-(4-p-methoxy-phenyl) propenyl phosphine) palladium, two (di-isopropyl-3-(4-dimethylaminophenyl) propenyl phosphine) palladium, two (di-isopropyl-3-(2-furyl) propenyl phosphine) palladium, two (di-isopropyl-3-(2-pyridyl) propenyl phosphine) palladium, two (di-isopropyl-3-(2-thienyl) propenyl phosphine) palladium, two (dicyclohexyl crot(on)yl phosphine) palladium, two (dicyclohexyl prenyl phosphine) palladium, two (dicyclohexyl-pentenyl phosphine) palladium, two (dicyclohexyl-5-methyl-2-hexenyl phosphine) palladium, two (dicyclohexyl-3-cyclohexyl-2-propenyl phosphine) palladium, two (the fluoro-crotyl phosphine of dicyclohexyl-4-) palladium, two (dicyclohexyl-4-methoxyl group-crotyl phosphine) palladium, two (dicyclohexyl-4-dimethylamino-crotyl phosphine) palladium, two (dicyclohexyl-2,4-hexadienyl phosphine) palladium, two (own-4-alkynes-1-base phosphine of dicyclohexyl-2-) palladium, two (dicyclohexyl cinnamyl phosphine) palladium, two (dicyclohexyl-3-(4-fluorophenyl) propenyl phosphine) palladium, two (dicyclohexyl-3-(4-p-methoxy-phenyl) propenyl phosphine) palladium, two (dicyclohexyl-3-(4-dimethylaminophenyl) propenyl phosphine) palladium, two (dicyclohexyl-3-(2-furyl) propenyl phosphine) palladium, two (dicyclohexyl-3-(2-pyridyl) propenyl phosphine) palladium, two (dicyclohexyl-3-(2-thienyl) propenyl phosphine) palladium, two (di-t-butyl crot(on)yl phosphine) palladium, two (di-t-butyl prenyl phosphine) palladium, two (di-t-butyl-pentenyl phosphine) palladium, two (di-t-butyl-5-methyl-2-hexenyl phosphine) palladium, two (di-t-butyl-3-cyclohexyl-2-propenyl phosphine) palladium, two (the fluoro-crotyl phosphine of di-t-butyl-4-) palladium, two (di-t-butyl-4-methoxyl group-crotyl phosphine) palladium, two (di-t-butyl-4-dimethylamino-crotyl phosphine) palladium, two (di-t-butyl-2,4-hexadienyl phosphine) palladium, two (own-4-alkynes-1-base phosphine of di-t-butyl-2-) palladium, two (di-t-butyl cinnamyl phosphine) palladium, two (di-t-butyl-3-(4-fluorophenyl) propenyl phosphine) palladium, two (di-t-butyl-3-(4-p-methoxy-phenyl) propenyl phosphine) palladium, two (di-t-butyl-3-(4-dimethylaminophenyl) propenyl phosphine) palladium, two (di-t-butyl-3-(2-furyl) propenyl phosphine) palladium, two (di-t-butyl-3-(2-pyridyl) propenyl phosphine) palladium, two (di-t-butyl-3-(2-thienyl) propenyl phosphine) palladium, two (di-isopropyl crot(on)yl phosphine) palladium chloride, two (di-isopropyl prenyl phosphine) palladium chloride, two (two (di-isopropyl-pentenyl phosphine) palladium chloride, two (di-isopropyl-5-methyl-2-hexenyl phosphine) palladium chloride, two (di-isopropyl-3-cyclohexyl-2-propenyl phosphine) palladium chloride, two (the fluoro-crotyl phosphine of di-isopropyl-4-) palladium chloride, two (di-isopropyl-4-methoxyl group-crotyl phosphine) palladium chloride, two (di-isopropyl-4-dimethylamino-crotyl phosphine) palladium chloride, two (di-isopropyl-2,4-hexadienyl phosphine) palladium chloride, two (own-4-alkynes-1-base phosphine of di-isopropyl-2-) palladium chloride, two (di-isopropyl cinnamyl phosphine) palladium chloride, two (di-isopropyl-3-(4-fluorophenyl) propenyl phosphine) palladium chloride, two (di-isopropyl-3-(4-p-methoxy-phenyl) propenyl phosphine) palladium chloride, two (di-isopropyl-3-(4-dimethylaminophenyl) propenyl phosphine) palladium chloride, two (di-isopropyl-3-(2-furyl) propenyl phosphine) palladium chloride, two (di-isopropyl-3-(2-pyridyl) propenyl phosphine) palladium chloride, two (di-isopropyl-3-(2-thienyl) propenyl phosphine) palladium chloride, two (dicyclohexyl crot(on)yl phosphine) palladium chloride, two (dicyclohexyl prenyl phosphine) palladium chloride, two (dicyclohexyl-pentenyl phosphine) palladium chloride, two (dicyclohexyl-5-methyl-2-hexenyl phosphine) palladium chloride, two (dicyclohexyl-3-cyclohexyl-2-propenyl phosphine) palladium chloride, two (the fluoro-crotyl phosphine of dicyclohexyl-4-) palladium chloride, two (dicyclohexyl-4-methoxyl group-crotyl phosphine) palladium chloride, two (dicyclohexyl-4-dimethylamino-crotyl phosphine) palladium chloride, two (dicyclohexyl-2,4-hexadienyl phosphine) palladium chloride, two (own-4-alkynes-1-base phosphine of dicyclohexyl-2-) palladium chloride, two (dicyclohexyl cinnamyl phosphine) palladium chloride, two (dicyclohexyl-3-(4-fluorophenyl) propenyl phosphine) palladium chloride, two (dicyclohexyl-3-(4-p-methoxy-phenyl) propenyl phosphine) palladium chloride, two (dicyclohexyl-3-(4-dimethylaminophenyl) propenyl phosphine) palladium chloride, two (dicyclohexyl-3-(2-furyl) propenyl phosphine) palladium chloride, two (dicyclohexyl-3-(2-pyridyl) propenyl phosphine) palladium chloride, two (dicyclohexyl-3-(2-thienyl) propenyl phosphine) palladium chloride, two (di-t-butyl crot(on)yl phosphine) palladium chloride, two (di-t-butyl prenyl phosphine) palladium chloride, two (di-t-butyl-pentenyl phosphine) palladium chloride, two (di-t-butyl-5-methyl-2-hexenyl phosphine) palladium chloride, two (di-t-butyl-3-cyclohexyl-2-propenyl phosphine) palladium chloride, two (the fluoro-crotyl phosphine of di-t-butyl-4-) palladium chloride, two (di-t-butyl-4-methoxyl group-crotyl phosphine) palladium chloride, two (di-t-butyl-4-dimethylamino-crotyl phosphine) palladium chloride, two (di-t-butyl-2,4-hexadienyl phosphine) palladium chloride, two (own-4-alkynes-1-base phosphine of di-t-butyl-2-) palladium chloride, two (di-t-butyl cinnamyl phosphine) palladium chloride, two (di-t-butyl-3-(4-fluorophenyl) propenyl phosphine) palladium chloride, two (di-t-butyl-3-(4-p-methoxy-phenyl) propenyl phosphine) palladium chloride, two (di-t-butyl-3-(4-dimethylaminophenyl) propenyl phosphine) palladium chloride, two (di-t-butyl-3-(2-furyl) propenyl phosphine) palladium chloride, two (di-t-butyl-3-(2-pyridyl) propenyl phosphine) palladium chloride, two (di-t-butyl-3-(2-thienyl) propenyl phosphine) palladium chloride, two (di-isopropyl crot(on)yl phosphine) Nickel Chloride, two (di-isopropyl prenyl phosphine) Nickel Chloride, two (two (di-isopropyl-pentenyl phosphine) Nickel Chloride, two (di-isopropyl-5-methyl-2-hexenyl phosphine) Nickel Chloride, two (di-isopropyl-3-cyclohexyl-2-propenyl phosphine) Nickel Chloride, two (the fluoro-crotyl phosphine of di-isopropyl-4-) Nickel Chloride, two (di-isopropyl-4-methoxyl group-crotyl phosphine) Nickel Chloride, two (di-isopropyl-4-dimethylamino-crotyl phosphine) Nickel Chloride, two (di-isopropyl-2,4-hexadienyl phosphine) Nickel Chloride, two (own-4-alkynes-1-base phosphine of di-isopropyl-2-) Nickel Chloride, two (di-isopropyl cinnamyl phosphine) Nickel Chloride, two (di-isopropyl-3-(4-fluorophenyl) propenyl phosphine) Nickel Chloride, two (di-isopropyl-3-(4-p-methoxy-phenyl) propenyl phosphine) Nickel Chloride, two (di-isopropyl-3-(4-dimethylaminophenyl) propenyl phosphine) Nickel Chloride, two (di-isopropyl-3-(2-furyl) propenyl phosphine) Nickel Chloride, two (di-isopropyl-3-(2-pyridyl) propenyl phosphine) Nickel Chloride, two (di-isopropyl-3-(2-thienyl) propenyl phosphine) Nickel Chloride, two (dicyclohexyl crot(on)yl phosphine) Nickel Chloride, two (dicyclohexyl prenyl phosphine) Nickel Chloride, two (dicyclohexyl-pentenyl phosphine) Nickel Chloride, two (dicyclohexyl-5-methyl-2-hexenyl phosphine) Nickel Chloride, two (dicyclohexyl-3-cyclohexyl-2-propenyl phosphine) Nickel Chloride, two (the fluoro-crotyl phosphine of dicyclohexyl-4-) Nickel Chloride, two (dicyclohexyl-4-methoxyl group-crotyl phosphine) Nickel Chloride, two (dicyclohexyl-4-dimethylamino-crotyl phosphine) Nickel Chloride, two (dicyclohexyl-2,4-hexadienyl phosphine) Nickel Chloride, two (own-4-alkynes-1-base phosphine of dicyclohexyl-2-) Nickel Chloride, two (dicyclohexyl cinnamyl phosphine) Nickel Chloride, two (dicyclohexyl-3-(4-fluorophenyl) propenyl phosphine) Nickel Chloride, two (dicyclohexyl-3-(4-p-methoxy-phenyl) propenyl phosphine) Nickel Chloride, two (dicyclohexyl-3-(4-dimethylaminophenyl) propenyl phosphine) Nickel Chloride, two (dicyclohexyl-3-(2-furyl) propenyl phosphine) Nickel Chloride, two (dicyclohexyl-3-(2-pyridyl) propenyl phosphine) Nickel Chloride, two (dicyclohexyl-3-(2-thienyl) propenyl phosphine) Nickel Chloride, two (di-t-butyl crot(on)yl phosphine) Nickel Chloride, two (di-t-butyl prenyl phosphine) Nickel Chloride, two (di-t-butyl-pentenyl phosphine) Nickel Chloride, two (di-t-butyl-5-methyl-2-hexenyl phosphine) Nickel Chloride, two (di-t-butyl-3-cyclohexyl-2-propenyl phosphine) Nickel Chloride, two (the fluoro-crotyl phosphine of di-t-butyl-4-) Nickel Chloride, two (di-t-butyl-4-methoxyl group-crotyl phosphine) Nickel Chloride, two (di-t-butyl-4-dimethylamino-crotyl phosphine) Nickel Chloride, two (di-t-butyl-2,4-hexadienyl phosphine) Nickel Chloride, two (own-4-alkynes-1-base phosphine of di-t-butyl-2-) Nickel Chloride, two (di-t-butyl cinnamyl phosphine) Nickel Chloride, two (di-t-butyl-3-(4-fluorophenyl) propenyl phosphine) Nickel Chloride, two (di-t-butyl-3-(4-p-methoxy-phenyl) propenyl phosphine) Nickel Chloride, two (di-t-butyl-3-(4-dimethylaminophenyl) propenyl phosphine) Nickel Chloride, two (di-t-butyl-3-(2-furyl) propenyl phosphine) Nickel Chloride, two (di-t-butyl-3-(2-pyridyl) propenyl phosphine) Nickel Chloride, two (di-t-butyl-3-(2-thienyl) propenyl phosphine) Nickel Chloride.
Preferably two (di-t-butyl crot(on)yl phosphine) palladium, two (di-t-butyl prenyl phosphine) palladium, two (di-t-butyl crot(on)yl phosphine) palladium chloride, two (di-t-butyl prenyl phosphine) palladium chloride, two (di-t-butyl crot(on)yl phosphine) Nickel Chloride, two (di-t-butyl prenyl phosphine) Nickel Chloride.
The phosphine compound used uses distillation product, recrystallization product usually, also can use reaction solution, or in its concentrate, reaction solution, adds acid carry out quaternary thus add the upper strata that alkali and solvent obtain after being heated up in a steamer on upper strata again.Described coordination compound is by known method or manufacture in advance according to the method, is then used in catalyzed reaction.
In addition, as described in Example 11, also transistion metal compound can be added in catalyzed reaction together with phosphine compound, phosphonium salt and use.Now, transistion metal compound can with the alkali reaction in phosphine compound, reaction solution thus with become the coordination of phosphine compound phosphonium salt, thus carry out the reaction identical with above-mentioned catalyzed reaction.
As the example of the nickel compound shown in transistion metal compound, nickelous chloride (II), nickel acetate (II), acetopyruvic acid nickel (II), nickel oxide (II), two (cyclooctadiene) nickel (0) etc. can be enumerated.In addition, as the example of iron cpd, iron(ic) chloride (II) (FeCl can be enumerated 2), iron(ic) chloride (III) (FeCl 3) etc. iron halide.But, be not limited to above-mentioned example.
In the compound used as transistion metal compound, as the example of used palladium compound, palladium (II) can be used, Palladous chloride (II), palladium bromide (II), palladium tetrachloride (II) sour sodium, acetopyruvic acid palladium (II), Er Ya Benzyl benzylacetone acid palladium (0) title complex, tetrakis triphenylphosphine palladium (0), two (tri-o-tolyl phosphine) palladium (0), propionic acid palladium (II), (cyclooctadiene-1, 5) palladium chloride (II), palladium (0)-diallyl ether title complex, Palladous nitrate (II), two (acetonitrile) Palladous chloride (II), two (cyanophenyl) Palladous chloride (II) and other palladium (0) title complex and palladium (II) title complex.
When manufacturing described coordination compound in advance, in water or organic solvent or their mixed solvent, carry out reaction by making the phosphine compound shown in general formula (1) and transition metal or transistion metal compound and easily manufacture.Such as, two (the di-t-butyl crot(on)yl phosphine) palladium chlorides shown in general formula (4) by adding the methanol solution of palladium tetrachloride (II) sour sodium and carrying out heating as required synthesizing in the solution of di-t-butyl crot(on)yl phosphine.As spendable reaction solvent, water can be enumerated, the alcoholic solvent of methyl alcohol, ethanol, propyl alcohol etc., the aliphatic category solvent of hexane, heptane etc., the aromatic series kind solvent of benzene, toluene etc., the halogen based solvents of methylene dichloride, chloroform etc., the nitrile solvents of acetonitrile, cyanophenyl etc., the ether solvents of tetrahydrofuran (THF), diethyl ether etc., above-mentioned mixed solvent.
(phosphonium salt compound)
Zuo is phosphonium salt compound, preferably particularly R in general formula (6) 1and R 2for the tertiary butyl, Y -for B -f 4or B -ph 4phosphonium salt.Y -for B -f 4organic layer by adding 40% fluoborate aqueous solution in the phosphine compound of the general formula (1) with dchloromethane, thus concentrates and synthesizes by phosphonium salt.In addition, general formula (1) even if phosphine compound use its manufacture in reaction solution also no problem, when solvability is low, after adding 40% fluoborate aqueous solution, remove organic layer, carry out extracting with the halogen based solvents of methylene dichloride etc. afterwards.In addition, also can similarly synthesize even if pass through to add Tetrafluoroboric acid sodium water solution in the quaternary salt be made up of the acid such as hydrochloric acid, sulfuric acid at the phosphine compound of general formula (1).Y -for B -ph 4phosphonium salt add tetraphenylboronic acid sodium water solution to synthesize by the quaternary salt that forms of the acid such as hydrochloric acid, sulfuric acid by the phosphine compound at general formula (1).
(using method of catalyzer)
Typically, as the catalytic amount used, can use in the scope of 0.001 ~ 50 % by mole relative to matrix.Preferably 0.01 ~ 10 % by mole, more preferably 0.01 ~ 5 % by mole.As long as Phosphine ligands relative to transition metal for wait mole more than, the ratio of transition metal and part can use in the scope of 1:1 ~ 1:100.The ratio of preferred transition metal and part is 1:1 ~ 1:10, the particularly preferably scope of 1:1 ~ 1:5.Tight transition metal/part the ratio that should use depends on specific purposes, also depends on the amount of used catalyzer in addition.So typically, when transiting metal concentration very low (< 0.01 % by mole), the transition metal/part ratio of the situation lower than transiting metal concentration preferably using the transition metal of 0.5 ~ 0.01 % by mole such.
This catalyzer uses favourable in the linked reaction forming C-C key or C-heteroatomic bond.Such as, but to those skilled in the art, the known reaction by other transition metal institute catalysis, the hydrogenation of metathesis (metathesis) reaction or double bond or carbonyl compound also carrys out catalysis by this catalyzer.
(manufacture method of aromatic amines compound)
The invention reside in the manufacture method of providing package containing the aromatic amines compound of following content, namely in organic solvent, under the existence of transition-metal catalyst and alkali, make halogen atom and/or there is the aromatics of reactive behavior base and primary amine and/or secondary amine to react, as shown in following reaction formula.
In formula, Ar 1expression can have substituent aromatic hydrocarbyl, maybe can have substituent aromatic heterocycle, and X represents reactive behavior base.As the example of X, chlorine atom can be enumerated, bromine atoms, atomic iodine or sulfonate group, specifically, can illustrate bromobenzene, 2-bromobenzene ether, 3-bromobenzene ether, 4-bromobenzene ether, 2 bromo toluene, 3-toluene bromide, 4-toluene bromide, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2-bromoxynil, 3-bromoxynil, 4-bromoxynil, 2-5 bromine benzotrifluoride, 3-5 bromine benzotrifluoride, 4-5 bromine benzotrifluoride, bromo-2, the 4-dimethoxy benzenes of 1-, bromo-2, the 5-dimethoxy benzenes of 1-, 2-bromophenethyl alcohol, 3-bromophenethyl alcohol, 4-bromophenethyl alcohol, the bromo-1，2，4-trimethylbenzene of 5-, bromo-1, the 3-dimethylbenzene of 2-, bromo-Isosorbide-5-Nitrae-the dimethylbenzene of 2-, 3-bromo-1,2-xylene, 4-bromo-1,2-xylene, bromo-1, the 3-dimethylbenzene of 4-, bromo-1, the 3-dimethylbenzene of 5-, the bromo-3-of 1-(trifluoromethoxy) benzene, the bromo-4-of 1-(trifluoromethoxy) benzene, 2-bromo biphenyl, 3-bromo biphenyl, 4-bromo biphenyl, 4-bromo-1,2-(methylene-dioxy) benzene, 1-bromonaphthalene, 2-bromonaphthalene, the bromo-2-methylnaphthalene of 1-, the bromo-4-methylnaphthalene of 1-, the bromo-9H-fluorenes of 1-, the aryl bromide class of the bromo-9H-fluorenes of 2-etc., chlorobenzene, 2-chloroneb, 3-chloroneb, 4-chloroneb, 2-toluene(mono)chloride, 3-toluene(mono)chloride, 4-toluene(mono)chloride, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-6-chlorophenyl nitrile, 3-6-chlorophenyl nitrile, 4-6-chlorophenyl nitrile, 2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride, 4-chlorobenzotrifluoride, 1-chloro-2, 4-dimethoxy benzene, 1-chloro-2, 5-dimethoxy benzene, 2-chlorophenethylol, 3-chlorophenethylol, 4-chlorophenethylol, 5-chloro-1, 2, 4-Three methyl Benzene, 2-chloro-1, 3-dimethylbenzene, 2-chloro-1, 4-dimethylbenzene, 3-chloro-1, 2-dimethylbenzene, 4-chloro-1, 2-dimethylbenzene, 4-chloro-1, 3-dimethylbenzene, 5-chloro-1, 3-dimethylbenzene, the chloro-3-of 1-(trifluoromethoxy) benzene, the chloro-4-of 1-(trifluoromethoxy) benzene, 2-chlordiphenyl, 3-chlordiphenyl, 4-chlordiphenyl, 4-chloro-1, 2-(methylene-dioxy) benzene, the chloro-naphthalene of 1-, the chloro-naphthalene of 2-, 1-chloro-2-methyl naphthalene, the chloro-4-methylnaphthalene of 1-, the chloro-9H-fluorenes of 1-, the aryl chloride class of the chloro-9H-fluorenes of 2-etc., iodobenzene, 2-iodanisol, 3-iodanisol, 4-iodanisol, 2-toluene iodide, 3-toluene iodide, 4-toluene iodide, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2-ioxynil, 3-ioxynil, 4-ioxynil, 2-iodine phenylfluoroform, 3-iodine phenylfluoroform, 4-iodine phenylfluoroform, 1-iodo-2, 4-dimethoxy benzene, 1-iodo-2, 5-dimethoxy benzene, 2-iodobenzene ethanol, 3-iodobenzene ethanol, 4-iodobenzene ethanol, 5-iodo-1, 2, 4-Three methyl Benzene, 2-iodo-1, 3-dimethylbenzene, 2-iodo-1, 4-dimethylbenzene, 3-iodo-1, 2-dimethylbenzene, 4-iodo-1, 2-dimethylbenzene, 4-iodo-1, 3-dimethylbenzene, 5-iodo-1, 3-dimethylbenzene, the iodo-3-of 1-(trifluoromethoxy) benzene, the iodo-4-of 1-(trifluoromethoxy) benzene, 2-iodine biphenyl, 3-iodine biphenyl, 4-iodine biphenyl, 4-iodo-1, 2-(methylene-dioxy) benzene, the iodo-naphthalene of 1-, the iodo-naphthalene of 2-, the iodo-2-methylnaphthalene of 1-, the aryl iodide class of the iodo-4-methylnaphthalene of 1-etc., fluorobenzene, 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2-toluene fluoride, 3-toluene fluoride, 4-toluene fluoride, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-fluorobenzonitrile, 3-fluorobenzonitrile, 4-fluorobenzonitrile, 2-fluoride trifluoro toluene, 3-fluoride trifluoro toluene, 4-fluoride trifluoro toluene, 1-fluoro-2, 4-dimethoxy benzene, 1-fluoro-2, 5-dimethoxy benzene, 2-fluorobenzene ethanol, 3-fluorobenzene ethanol, 4-fluorobenzene ethanol, 5-fluoro-1, 2, 4-Three methyl Benzene, 2-fluoro-1, 3-dimethylbenzene, 2-fluoro-1, 4-dimethylbenzene, 3-fluoro-1, 2-dimethylbenzene, 4-fluoro-1, 2-dimethylbenzene, 4-fluoro-1, 3-dimethylbenzene, 5-fluoro-1, 3-dimethylbenzene, the fluoro-3-of 1-(trifluoromethoxy) benzene, the fluoro-4-of 1-(trifluoromethoxy) benzene, 2-fluorine biphenyl, 3-fluorine biphenyl, 4-fluorine biphenyl, 4-fluoro-1, 2-(methylene-dioxy) benzene, the fluoro-naphthalene of 1-, the fluoro-naphthalene of 2-, the fluoro-2-methylnaphthalene of 1-, the aryl fluoride class of the fluoro-4-methylnaphthalene of 1-etc., as aromatic yl sulphonate, such as, trifluoro-methanesulfonyl oxy benzene can be illustrated, 2-trifluoro-methanesulfonyl oxy methyl-phenoxide, 3-trifluoro-methanesulfonyl oxy methyl-phenoxide, 4-trifluoro-methanesulfonyl oxy methyl-phenoxide, 2-trifluoro-methanesulfonyl oxy toluene, 3-trifluoro-methanesulfonyl oxy toluene, 4-trifluoro-methanesulfonyl oxy toluene, 2-trifluoro-methanesulfonyl oxy phenol, 3-trifluoro-methanesulfonyl oxy phenol, 4-trifluoro-methanesulfonyl oxy phenol, 2-trifluoro-methanesulfonyl oxy cyanophenyl, 3-trifluoro-methanesulfonyl oxy cyanophenyl, 4-trifluoro-methanesulfonyl oxy cyanophenyl, 2-trifluoro-methanesulfonyl oxy phenylfluoroform, 3-trifluoro-methanesulfonyl oxy phenylfluoroform, 4-trifluoro-methanesulfonyl oxy phenylfluoroform, 1-trifluoro-methanesulfonyl oxy-2,4-dimethoxy benzene, 1-trifluoro-methanesulfonyl oxy-2,5-dimethoxy benzene, 2-trifluoro-methanesulfonyl oxy phenylethyl alcohol, 3-trifluoro-methanesulfonyl oxy phenylethyl alcohol, 4-trifluoro-methanesulfonyl oxy phenylethyl alcohol, 5-trifluoro-methanesulfonyl oxy-1，2，4-trimethylbenzene, 2-trifluoro-methanesulfonyl oxy-1,3-dimethylbenzene, 2-trifluoro-methanesulfonyl oxy-Isosorbide-5-Nitrae-dimethylbenzene, 3-trifluoro-methanesulfonyl oxy-1,2-dimethylbenzene, 4-trifluoro-methanesulfonyl oxy-1,2-dimethylbenzene, 4-trifluoro-methanesulfonyl oxy-1,3-dimethylbenzene, 5-trifluoro-methanesulfonyl oxy-1,3-dimethylbenzene, 1-trifluoro-methanesulfonyl oxy-3-(trifluoromethoxy) benzene, 1-trifluoro-methanesulfonyl oxy-4-(trifluoromethoxy) benzene, 2-trifluoro-methanesulfonyl oxy biphenyl, 3-trifluoro-methanesulfonyl oxy biphenyl, 4-trifluoro-methanesulfonyl oxy biphenyl, 4-trifluoro-methanesulfonyl oxy-1,2-(methylene-dioxy) benzene, 1-trifluoro-methanesulfonyl oxy naphthalene, 2-trifluoro-methanesulfonyl oxy naphthalene, 1-trifluoro-methanesulfonyl oxy-2-methylnaphthalene, the aryl trifluoromethayl sulfonic acid ester class of 1-trifluoro-methanesulfonyl oxy-4-methylnaphthalene etc., mesyloxy benzene, 2-mesyloxy methyl-phenoxide, 3-mesyloxy methyl-phenoxide, 4-mesyloxy methyl-phenoxide, 2-mesyloxy toluene, 3-mesyloxy toluene, 4-mesyloxy toluene, 2-mesyloxy phenol, 3-mesyloxy phenol, 4-mesyloxy phenol, 2-mesyloxy cyanophenyl, 3-mesyloxy cyanophenyl, 4-mesyloxy cyanophenyl, 2-mesyloxy phenylfluoroform, 3-mesyloxy phenylfluoroform, 4-mesyloxy phenylfluoroform, 1-mesyloxy-2,4-dimethoxy benzene, 1-mesyloxy-2,5-dimethoxy benzene, 2-mesyloxy phenylethyl alcohol, 3-mesyloxy phenylethyl alcohol, 4-mesyloxy phenylethyl alcohol, 5-mesyloxy-1，2，4-trimethylbenzene, 2-mesyloxy-1,3-dimethylbenzene, 2-mesyloxy-Isosorbide-5-Nitrae-dimethylbenzene, 3-mesyloxy-1,2-dimethylbenzene, 4-mesyloxy-1,2-dimethylbenzene, 4-mesyloxy-1,3-dimethylbenzene, 5-mesyloxy-1,3-dimethylbenzene, 1-mesyloxy-3-(trifluoromethoxy) benzene, 1-mesyloxy-4-(trifluoromethoxy) benzene, 2-mesyloxy biphenyl, 3-mesyloxy biphenyl, 4-mesyloxy biphenyl, 4-mesyloxy-1,2-(methylene-dioxy) benzene, 1-mesyloxy naphthalene, 2-mesyloxy naphthalene, 1-mesyloxy-2-methylnaphthalene, the aryl methanesulfonate esters class of 1-mesyloxy-4-methylnaphthalene etc., tolysulfonyl oxygen base benzene, 2-(tolysulfonyl oxygen base) methyl-phenoxide, 3-(tolysulfonyl oxygen base) methyl-phenoxide, 4-(tolysulfonyl oxygen base) methyl-phenoxide, 2-(tolysulfonyl oxygen base) toluene, 3-(tolysulfonyl oxygen base) toluene, 4-(tolysulfonyl oxygen base) toluene, 2-(tolysulfonyl oxygen base) phenol, 3-(tolysulfonyl oxygen base) phenol, 4-(tolysulfonyl oxygen base) phenol, 2-(tolysulfonyl oxygen base) cyanophenyl, 3-(tolysulfonyl oxygen base) cyanophenyl, 4-(tolysulfonyl oxygen base) cyanophenyl, 2-(tolysulfonyl oxygen base) phenylfluoroform, 3-(tolysulfonyl oxygen base) phenylfluoroform, 4-(tolysulfonyl oxygen base) phenylfluoroform, 1-(tolysulfonyl oxygen base)-2,4-dimethoxy benzenes, 1-(tolysulfonyl oxygen base)-2,5-dimethoxy benzenes, 2-(tolysulfonyl oxygen base) phenylethyl alcohol, 3-(tolysulfonyl oxygen base) phenylethyl alcohol, 4-(tolysulfonyl oxygen base) phenylethyl alcohol, 5-(tolysulfonyl oxygen base)-1，2，4-trimethylbenzene, 2-(tolysulfonyl oxygen base)-1,3-dimethylbenzene, 2-(tolysulfonyl oxygen base)-Isosorbide-5-Nitrae-dimethylbenzene, 3-(tolysulfonyl oxygen base)-1,2-dimethylbenzene, 4-(tolysulfonyl oxygen base)-1,2-dimethylbenzene, 4-(tolysulfonyl oxygen base)-1,3-dimethylbenzene, 5-(tolysulfonyl oxygen base)-1,3-dimethylbenzene, 1-(tolysulfonyl oxygen base)-3-(trifluoromethoxy) benzene, 1-(tolysulfonyl oxygen base)-4-(trifluoromethoxy) benzene, 2-(tolysulfonyl oxygen base) biphenyl, 3-(tolysulfonyl oxygen base) biphenyl, 4-(tolysulfonyl oxygen base) biphenyl, 4-(tolysulfonyl oxygen base)-1,2-(methylene-dioxy) benzene, 1-(tolysulfonyl oxygen base) naphthalene, 2-(tolysulfonyl oxygen base) naphthalene, 1-(tolysulfonyl oxygen base)-2-methylnaphthalene, the aryl p-toluenesulfonic esters class of 1-(tolysulfonyl oxygen base)-4-methylnaphthalene etc., Deng.In addition, 1, 2-dibromobenzene, 1, 3-dibromobenzene, 1, 4-dibromobenzene, 9, 10-dibromoanthracene, 9, 10-bis-chrloroanthracene, 4, 4 '-'-dibromobiphenyl, 4, 4 '-DCBP, 4, 4 '-iodine biphenyl, the bromo-2-fluorobenzene of 1-, the bromo-3-fluorobenzene of 1-, the bromo-4-fluorobenzene of 1-, the bromo-2-chlorobenzene of 1-, the bromo-3-chlorobenzene of 1-, the bromo-4-chlorobenzene of 1-, the bromo-5-toluene(mono)chloride of 2-, the bromo-4-chlorobenzotrifluoride of 3-, the bromo-2-chlorobenzotrifluoride of 5-, 1-bromo-2, 3-dichlorobenzene, 1-bromo-2, 6-dichlorobenzene, 1-bromo-3, 5-dichlorobenzene, the bromo-4-toluene fluoride of 2-, the bromo-5-toluene fluoride of 2-, the bromo-4-toluene fluoride of 3-, the bromo-2-toluene fluoride of 4-, 4-bromine-3-fluorine methylbenzene, 2, the bromo-9H-fluorenes of 7-bis-, 1, the bromo-9H-fluorenes of 8-bis-, 2, the chloro-9H-fluorenes of 7-bis-, 1, the chloro-9H-fluorenes of 8-bis-, 2-bromo-9, 9-dimethyl fluorene, 2, 7-bis-bromo-9, the aryl halide class with two or more halogen atom of 9-dimethyl fluorene etc., 1-chloro-2-trifluoro-methanesulfonyl oxy benzene, 1-chloro-3-trifluoro-methanesulfonyl oxy benzene, 1-chloro-4-trifluoro-methanesulfonyl oxy benzene, 9-chloro-10-trifluoro-methanesulfonyl oxy anthracene, 9-chloro-10-trifluoro-methanesulfonyl oxy anthracene, the chloro-4 '-trifluoro-methanesulfonyl oxy biphenyl of 4-, the iodo-4 '-trifluoro-methanesulfonyl oxy biphenyl of 4-, 1-bromo-2-mesyloxy benzene, 1-bromo-3-mesyloxy benzene, 1-bromo-4-mesyloxy benzene, 9-bromo-10-mesyloxy anthracene, 9-chloro-10-mesyloxy anthracene, the bromo-4 '-mesyloxy biphenyl of 4-, the chloro-4 '-mesyloxy biphenyl of 4-, the iodo-4 '-mesyloxy biphenyl of 4-, the bromo-2-of 1-(tolysulfonyl oxygen base) benzene, the bromo-3-of 1-(tolysulfonyl oxygen base) benzene, the bromo-4-of 1-(tolysulfonyl oxygen base) benzene, the bromo-10-of 9-(tolysulfonyl oxygen base) anthracene, the chloro-10-of 9-(tolysulfonyl oxygen base) anthracene, bromo-4 '-(the tolysulfonyl oxygen base) biphenyl of 4-, chloro-4 '-(the tolysulfonyl oxygen base) biphenyl of 4-, the aryl halide class respectively with more than 1 halogen atom and sulfonate group of iodo-4 '-(the tolysulfonyl oxygen base) biphenyl of 4-etc. also can be used as the aryl halide used in the present invention and illustrates.In addition, above-mentioned substance is not limited to.R 5and R 6or represent independently of one another hydrogen atom (but, R 5and R 6be asynchronously hydrogen atom), the aliphatic alkyl of substituent straight-chain or branched can be had, aromatic heterocycle that the aliphatic alkyl can with substituent monocycle or polycycle, the aromatic hydrocarbyl can with substituent monocycle or polycycle maybe can have substituent monocycle or polycycle, or also can be R 5with R 6form identical ring structure, and nitrogen-atoms in this ring participates in the such R of the carbazole, piperidines, morpholine etc. of reaction 5, R 6and the condensation heterocycle of nitrogen-atoms condensation.As amine used in the present invention, such as, ethamine, propylamine, Isopropylamine, butylamine, isobutylamine, sec-butylamine, TERTIARY BUTYL AMINE, amylamine, isobutylcarbylamine, neopentyl amine, hexylamine, 2 ethyl hexylamine, cyclopropylamine, cyclopentamine, hexahydroaniline, heptyl amice, octylame, amantadine, benzylamine, Alpha-Methyl benzylamine, α can be enumerated, alpha-alpha-dimethyl benzylamine, 2-phenyl-ethyl amine, 2-methoxyethyl amine, 2-ethoxy ethyl amine, 2-methoxy propanamine, 3 methoxypropyl amine etc. can have substituent Armeen class, aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromaniline, 3-bromaniline, 4-bromaniline, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-methyl oxyaniline, 3-methyl oxyaniline, 4-methyl oxyaniline, 2-Tolylamine, 3-Tolylamine, 4-Tolylamine, 2,3-xylidene(s), toluene 24 diamine, 2,6-xylidene(s), 3,5-xylidene(s), 2，4，6-trimethyl aniline, 2,3-dichlorphenamide bulk powder, 2,4 dichloro aniline, 2,5-dichlorphenamide bulk powder, 2,6-DCA, 3,5-dichlorphenamide bulk powder, 2,3-difluoroaniline, 2,4 difluorobenzene amine, 2,6-difluoroaniline, the chloro-3-fluoroaniline of 2-, the chloro-4-fluoroaniline of 2-, the chloro-5-fluoroaniline of 2-, the chloro-6-fluoroaniline of 2-, the chloro-2-fluoroaniline of 3-, the chloro-4-fluoroaniline of 3-, the chloro-2-fluoroaniline of 4-, the chloro-2-fluoroaniline of 5-, the chloro-2-fluoroaniline of 6-, naphthalidine, 2-naphthylamines, 2-phenylaniline, 4-phenylaniline, Isosorbide-5-Nitrae-diaminobenzene, 4-dimethylaminoaniline, 4,4 '-benzidine etc. can have substituent primary aromatic amine class, PA, 3-aminopyridine, 4-aminopyridine, 2-aminopyrimidine, 4-aminopyrimidine, 3-amino-pyrazol, 5-amino-pyrazol, 3-aminotriazole, 5-aminotriazole, 2-amino indole, 3-amino indole, 2-quinolylamine, 3-quinolylamine, 4-quinolylamine, 7-quinolylamine, 8-quinolylamine, 9-amino anthracene etc. can have substituent heteroaromatic primary amine class, dimethylamine, diethylamine, Diisopropylamine, diisobutylamine, two TERTIARY BUTYL AMINE, two cyclopentamine, dicyclohexyl amine, methyl isopropylamine, ethyl isopropylamine, methyl-tert butylamine, methyl cyclohexylamine, N-methylbenzylamine, N, alpha-alpha-dimethyl benzylamine, N, α, α-trimethylammonium benzylamine, two-(2-ethylhexyl) amine, N-Methylphenethylamine etc. can have substituent aliphatic secondary amine, piperazine, 2-methylpiperazine, homopiperazine, N-methylhomopiperazin, 2,6-lupetazin, N methyl piperazine, NEP, N-ethoxycarbonylpiperazine, N-benzyl piperazine, morpholine, 3,5-thebaine, piperidines, 2,6-lupetidine, 2,2-lupetidine, 3,5-lupetidine, 2-ethyl piperidine, 4-piperidone condensed ethandiol, tetramethyleneimine, 2,5-dimethyl pyrrolidines etc. can have substituent assorted aliphatics cyclic amine, pyrroles, indoles, pyrazoles, imidazoles, 1,2,4-triazole, carbazole etc. can have substituent heteroaromatic cyclic amine, methylphenylamine, N-ethylaniline, N-isopropyl aniline, N-tertiary butyl aniline, N-methyl isophthalic acid-naphthylamines, N-methyl-2-naphthylamines, 2-dimethylaminopyridine, 3-dimethylaminopyridine, 2-methylaminopyrimidin, N, N '-diphenyl-phenylene-diamine, N, N-pentanoic etc. can have substituent aromatic amine class on aromatic nucleus, Deng, in addition, be not limited to above-mentioned substance.
In manufacture method of the present invention, preferably react under the existence (coexisting) of alkali.As alkali, such as, the mineral alkali of sodium carbonate, salt of wormwood, cesium carbonate, sodium hydroxide, potassium hydroxide, potassiumphosphate etc. can be enumerated, the organo-metallic alkali of butyllithium, phenyl lithium, methylmagnesium-chloride, phenyl-magnesium-chloride etc., the metal amide of sodium hexamethyldisilazide and LHMDS etc., sodium tert-butoxide, potassium tert.-butoxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, (2,4,6-tri-butyl-phenol) sodium, (2,4,6-tri-butyl-phenol) metal alkoxide etc. of potassium etc.Preferably can enumerate metal alkoxide, more preferably can enumerate the alkali metal alcoholates of the alkoxy C 1 ~ C6 of sodium tert-butoxide, potassium tert.-butoxide etc.
In manufacture method of the present invention, preferably react in presence of organic solvent.As spendable organic solvent, aromatic hydrocarbon solvents, the tetrahydrofuran (THF), 1 of toluene, dimethylbenzene (o-Xylol, m-xylene, p-Xylol and their mixture), sym-trimethylbenzene, p-Methylisopropylbenzene, ethylbenzene, chlorobenzene, oil of mirbane etc. can be enumerated, the ether solvent of 4-dioxan etc. and their mixed solvent, preferred toluene, dimethylbenzene, sym-trimethylbenzene, ethylbenzene, chlorobenzene, oil of mirbane, more preferably toluene, dimethylbenzene, sym-trimethylbenzene, further preferred dimethylbenzene.
(manufacture method of aromatics)
The invention reside in the manufacture method of providing package containing the aromatics of following content, namely in a solvent, under transition-metal catalyst and alkali exist, make halogen atom and/or any one having in the aromatics of reactive behavior base and organoboron compound group is reacted, as shown in following reaction formula.
In formula, Ar 2expression can have substituent aromatic hydrocarbons maybe can have substituent aromatic heterocyclic compounds.In addition, X represents reactive behavior base, as an example, can enumerate chlorine atom, bromine atoms, atomic iodine or sulfonate group, can with Ar 1similarly illustrate.
In formula, R 7expression can have substituent alkyl, alkenyl, alkynyl etc. aliphatic alkyl, substituent aromatic hydrocarbyl can be had maybe can have substituent aromatic heterocycle, Y represents the counter cation of sodium, potassium etc.In addition, R 8represent that hydrogen atom maybe can have substituent alkyl, n represents the integer of 1 ~ 3.In addition, R 9substituent arylidene can be had, maybe can have substituent heterocyclic radical and maybe can have the atomic bonding of substituent alkylidene group as-OBO-, thus the ring comprising-OBO-can be formed.As boric acid used in the present invention, such as, the boron alkyl acids of methyl-boron-dihydroxide, ethyl-boron dihydroxide, cyclopropylboronic acid, butyl boron dihydroxide, cyclohexyl boric acid etc. can be enumerated; Vinyl boronic acids, 1-propylene-1-ylboronic acid, 1-propylene-2-ylboronic acid, 1-butylene-1-ylboronic acid, 1-butylene-2-ylboronic acid, 2-butylene-2-ylboronic acid, 1-amylene-1-ylboronic acid, α-vinylboronic acid, β-vinylboronic acid, 1, the alkenyl boric acid class of 2-diphenylethlene ylboronic acid, 2,2-diphenylethlene ylboronic acids, cyclopentenyl boric acid, cyclohexenyl boric acid, 2-methyl cyclohexane ene boric acid etc.; The alkynyl boric acid class of ethynyl boric acid, 3-methoxyl group-1-propine-1-ylboronic acid, cyclopropyl acethlene ylboronic acid, 1-pentynyl boric acid, 3,3-dimethyl-ethyl acetylene-1-ylboronic acid, 2-phenyl-1-ethynyl boric acid, 5-chloro-1-pentynyl boric acid, 2-(di-t-butyl dimethyl-silicon alkanol)-ethynyl boric acid etc.; As aryl boric acid, can enumerate phenyl-boron dihydroxide, other can enumerate the alkylaryl boric acid class of 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 4-trifluoromethyl phenyl boronic acid etc.; The boric acid class with hetero ring type base of 2-thienylboronic acid, 2-furyl boronic acid, 2-pyridinylboronic acid etc.; 2,3,4,5,6-pentafluorophenylboronic acid, 2-flurophenyl boronic acid, 3-flurophenyl boronic acid, 4-flurophenyl boronic acid, 2-chlorophenylboronic acid, 3-chlorophenylboronic acid, 4-chlorophenylboronic acid, 2-bromophenylboronic acid, 3-bromophenylboronic acid, 4-bromophenylboronic acid, 2-iodophenyl boronic acid, 3-iodophenyl boronic acid, 4-iodophenyl boronic acid, 2,4-difluorophenyl boronic acid, 3,4-difluorophenyl boronic acid, 2,3-difluorophenyl boronic acid, 3,4,5-trifluorophenylboronic acid, 2,3, the aryl boric acid class with halogen atom of 4-trifluorophenylboronic acid, 2,4,6-trifluorophenylboronic acid etc.; The aryl boric acid class with cyano group of 2-cyanophenyl boronic acid, 3-cyanophenyl boronic acid, 4-cyanophenyl boronic acid etc.; The alkoxy aromatic ylboronic acid class of 4-methoxyphenyl-boronic acid, 4-tert .-butoxyphenyl boric acid etc.; The polycycle aryl boric acid class of 1-naphthalene boronic acids, 9-luxuriant and rich with fragrance boric acid, 9-anthracene boric acid, ferrocenyl boric acid etc.; The hydroxyaryl boric acid class of 2-hydroxyphenyl boronic acid, 3-hydroxyphenyl boronic acid, 4-hydroxyphenyl boronic acid etc.; The aryl boric acid class with carbonyl substituted base of 4-acetylphenyl boronic acid, 4-formyl phenylboronic acid etc., but be not limited to above-mentioned substance.In addition, the ester class (such as, dimethyl ester, diethyl ester, dipropyl, pinacol ester etc.) etc. of above-mentioned boric acid can also similarly be enumerated.
Manufacture method of the present invention is preferably reacted under the existence of alkali (coexisting).Reaction can use any one in common mineral alkali, organic bases, as preferred alkali, such as, can enumerate the oxyhydroxide of sodium hydroxide, potassium hydroxide etc., such as sodium carbonate (Na 2cO 3), salt of wormwood (K 2cO 3), cesium carbonate (Cs 2cO 3) etc. carbonate, the acetate of such as sodium-acetate, Potassium ethanoate etc., such as sodium phosphate (Na 3pO 4), potassiumphosphate (K 3pO 4) etc. phosphoric acid salt, the organic salt etc. of the ammonium salt of such as triethylamine class, pyridine, morpholine, quinoline, piperidines, DBU (diazabicyclo undecylene), phenyl amines, tetra-n-butyl ammonium acetate etc. etc.Such alkali can be used alone, and in addition, but also two or more share.
In manufacture method of the present invention, usually can use solvent, preferably carry out in organic solvent.In addition, the solvent of water etc. can also be used.As organic solvent, the alcoholic solvent of methyl alcohol, ethanol etc. can be enumerated, N-Methyl pyrrolidone, N, dinethylformamide, N, the aprotic polar solvent of N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), acetonitrile etc., the ether solvents of diethyl ether, diisopropyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, Isosorbide-5-Nitrae-dioxan, tetrahydrofuran (THF) etc., the aromatic hydrocarbon solvents of benzene,toluene,xylene etc., the aliphatic hydrocarbon solvent etc. of hexane, heptane etc.
(other reactions)
The illustration of described linked reaction is not restricted to the kind of the linked reaction that can use catalyzer of the present invention, and in addition, the known catalyzer of the present invention of those skilled in the art can use in similar linked reaction as follows.
For being selected from the reaction of following each group:
(a) organo-tin compound and the Stille-cross-coupling of carbon electrophilic body as leavings group with halogen or class halogen;
The halogenide of (b) organosilane and aryl, heteroaryl or vinyl or the Hiyama-cross-coupling of Pseudohalides;
The halogenide of (c) organic zinc compound and aryl, heteroaryl or vinyl or the root bank-cross-coupling of Pseudohalides;
The halogenide of (d) Grignard Compound and aryl, heteroaryl or vinyl or the bear field-cross-coupling of Pseudohalides;
The halogenide of (e) terminal alkyne and aryl, heteroaryl or vinyl or the bacterium head-cross-coupling of Pseudohalides;
F alpha-aromatic that () is undertaken by enolate and the aryl of other stabilized carbanions or the halogenide of heteroaryl or Pseudohalides;
The halogenide of (g) aryl or heteroaryl or the cyanalation of Pseudohalides;
The halogenide of (h) aryl or heteroaryl or the carbonylation of Pseudohalides;
He Ke-the coupling in alkene of the halogenide of (i) aryl, heteroaryl or vinyl or Pseudohalides.
Embodiment
Whole pharmaceutical chemicalss is bought from sale supply source as reagent, as long as no special record, need not be further purified thus use.Tetrahydrofuran (THF) (THF) uses dehydrated solvent.Proton (1H) NMR (nuclear magnetic resonance map) carries out record with 400MHz respectively in JNM-ECS400 (Jeol Ltd.'s system).Chemical shift with Delta scale (δ) with every 1,000,000 part (ppm) represent, and in 1H NMR with reference to tetramethylsilane (δ=0ppm).
Below, specifically describe the present invention further according to embodiment, but the present invention is not limited to these embodiments.
In addition, below in an example, purity (%) is the area percentage value by gas chromatographic analysis.In addition, about the addition of copper compound, % by mole to represent relative to dialkyl group phosphonium chloride is merged.
[embodiment 1]
The manufacture of di-t-butyl crot(on)yl phosphine
Tetrahydrofuran (THF) 70ml, toluene 140ml, di-t-butylchlorophosphine 53.1g (0.28mol) and cupric chloride (I) 0.83g (0.0084mol (being equivalent to 3 % by mole)) is added in the four-hole boiling flask of 1L capacity fully having carried out nitrogen replacement.The temperature remaining on 10 DEG C ~ 20 DEG C dripped grignard reagent solution through 2 hours wherein, and this grignard reagent solution is prepared in tetrahydrofuran (THF) 327ml by crotyl chloride 27.9g (0.31mol) and MAGNESIUM METAL 15.0g (0.62mol) in advance.After being added dropwise to complete, stir 3 hours at the temperature of 10 DEG C ~ 20 DEG C.After reaction solution returns to 25 DEG C, confirm the disappearance of di-t-butylchlorophosphine by gas-chromatography.Thereafter, in reaction solution, add 3% aqueous sulfuric acid 62ml carry out separatory, then wash organic layer, and carry out drying by anhydrous sodium sulphate.Under reduced pressure heat up in a steamer desolventizing further, then distill, by the cut distillated in 80 DEG C under being collected in the decompression of 1.1torr (146.63Pa), thus obtain as sticky oil material the di-t-butyl crot(on)yl phosphine 31.0g (purity 97.0%) becoming target.Yield 54%.
Mass spectrum (EI method) M/Z 200(M+) 1H-NMR collection of illustrative plates (CDCl 3) δ ppm:1.14,1.15 (d, J=11.0Hz, 18H, (C h 3 c) 2-P-(cis body+trans body)), 1.62-1.73 (m, 3H ,-CH=CH-C h 3 (cis body+trans body)), 2.4 (br-s, 2H, (CH 3c) 2p-C h 2 -(cis body+trans body)), 5.39-5.74 (m, 2H ,-C h=C h-CH 3(cis body+trans body)),
[embodiment 2]
The manufacture of two (di-t-butyl crot(on)yl phosphine) palladium chloride
Hexane 11ml and di-t-butyl crot(on)yl phosphine 7.2g (0.036mol) is added in the four-hole boiling flask of 200ml capacity fully having carried out nitrogen replacement.Add the methanol solution 66.4g (0.018mol) of palladium tetrachloride acid (II) sodium wherein, reflux 10 minutes.Then, carry out after being cooled to 25 DEG C filtering and use methyl alcohol 27ml to clean.Obtained solid is carried out drying, thus obtains as yellow solid two (di-t-butyl crot(on)yl phosphine) the palladium chloride 9.8g becoming target.Yield 94%.
1H-NMR collection of illustrative plates (CDCl 3) δ ppm:1.49-1.53 (18H, C h 3 c) 2-P-(cis body+trans body)), 1.65-1.73 (m, 3H ,-CH=CH-C h 3 (cis body+trans body)), 2.88 (br-s, 2H, (CH 3c) 2p-C h 2 -(cis body+trans body)), 5.54-5.55 (m, 1H ,-CH=C h-CH 3(cis body+trans body)), 5.86-5.87 (m, 1H ,-C h=CH-CH 3(cis body+trans body)) molten point 180 DEG C (decomposition)
[embodiment 3]
The manufacture of di-t-butyl crotons Ji Phosphonium a tetrafluoro borate
Hexane 15ml and di-t-butyl crot(on)yl phosphine 4.0g (0.020mol) is added in the four-hole boiling flask of the 300ml capacity carrying out abundant nitrogen replacement.Add 40% fluoborate aqueous solution 4.38g (0.021mol) wherein to stir in 25 DEG C.Thereafter, in obtained lower floor, add toluene 30ml, after stirring in 25 DEG C, carry out separatory.Then in obtained lower floor, add methylene dichloride 30ml, stir in 25 DEG C.Obtained organic layer is under reduced pressure heated up in a steamer desolventizing, thus obtains as white solid the di-t-butyl crotons base Phosphonium a tetrafluoro borate 5.4g becoming target.Yield 95%.
1H-NMR collection of illustrative plates (D 2o) δ ppm:1.38,1.40 (d, J=16.7Hz, 18H, (C h 3 c) 2-P-(cis body+trans body)), 1.59-1.64 (m, 3H ,-CH=CH-C h 3 (cis body+trans body)), 3.10,3.13 (dd, J=12.5Hz, 7.4Hz, 2H, (CH 3c) 2p-C h 2 -(cis body+trans body)), 5.42-5.48 (m, 1H ,-CH=C h-CH 3(cis body+trans body)), 5.77-5.84 (m, 1H ,-C h=CH-CH 3(cis body+trans body)) molten point 110 DEG C
[embodiment 4]
The manufacture of di-t-butyl crotons Ji Phosphonium tetraphenyl borate salts
Tetrahydrofuran (THF) 2.7ml, toluene 5.5ml, di-t-butylchlorophosphine 7.1g (0.039mol) and cupric chloride (I) 0.12g (0.0012mol (being equivalent to 3 % by mole)) is added in the four-hole boiling flask of the 100ml capacity carrying out abundant nitrogen replacement.The temperature remaining on 30 DEG C ~ 45 DEG C wherein dripped grignard reagent solution through 20 minutes, and this grignard reagent solution is prepared in tetrahydrofuran (THF) 41ml by crotyl chloride 3.9g (0.043mol) and MAGNESIUM METAL 2.1g (0.086mol) in advance.After being added dropwise to complete, stir 3 hours at the temperature of 30 DEG C ~ 40 DEG C.After reaction solution returns to 25 DEG C, confirm the disappearance of di-t-butylchlorophosphine by gas-chromatography.Thereafter, in reaction solution, add 3% aqueous sulfuric acid 13ml carry out separatory, then wash organic layer.Then add 10% aqueous sulfuric acid 54ml to stir after 30 minutes and carry out separatory.After lower floor being cleaned with toluene 10ml, add hexane 15ml and 20% caustic soda aqueous solution 20ml stirs 30 minutes and carries out separatory.Upper strata carried out washing and loads 20% aqueous sulfuric acid 10.4g (0.021mol), stirring in 25 DEG C.Then, add 20% caustic soda (NaOH) aqueous solution 4.0g (0.020mol), stir in 25 DEG C.And then, add 18.7% tetraphenylboronic acid sodium water solution 11.5g (0.021mol), stir 10 minutes in 25 DEG C.Then filter, and clean with deionized water 255ml, methyl alcohol 142ml.Obtained solid is carried out drying, thus obtains as white solid the di-t-butyl crotons base Phosphonium tetraphenyl borate salts 8.4g becoming target.Yield 42%.
1H-NMR collection of illustrative plates (DMSO-d6) δ ppm:1.40,1.42 (d, J=16.5Hz, 18H, (C h 3 c) 2-P-(cis body+trans body)), 1.67-1.73 (m, 3H ,-CH=CH-C h 3 (cis body+trans body)), 3.33 (br=s, 2H, (CH 3c) 2p-C h 2 -(cis body+trans body)), 5.48-5.54 (m, 1H ,-CH=C h-CH 3(cis body+trans body)), 5.76-5.92 (m, 1H ,-C h=CH-CH 3(cis body+trans body)), 6.78 (t, J=7.10Hz, 4H, B- ph(cis body+trans body)), 6.92 (t, 8H, J=7.56Hz, B- ph(cis body+trans body)), 7.15-7.19 (m, 8H, B- ph(cis body+trans body)) molten point 169 DEG C
[embodiment 5]
The manufacture of two (di-t-butyl prenyl phosphine) palladium chloride
Tetrahydrofuran (THF) 5.3ml, toluene 5.5ml, di-t-butylchlorophosphine 9.5g (0.050mol) and cupric chloride (I) 0.15g (0.0015mol (being equivalent to 3 % by mole)) is added in the four-hole boiling flask of the 100ml capacity carrying out abundant nitrogen replacement.The temperature remaining on 30 DEG C ~ 40 DEG C wherein dripped grignard reagent solution through 1 hour, and this grignard reagent solution is prepared in tetrahydrofuran (THF) 119ml by prenyl chlorine 5.8g (0.055mol) and MAGNESIUM METAL 2.7g (0.11mol) in advance.After being added dropwise to complete, stir 1 hour at the temperature of 30 DEG C ~ 40 DEG C.After reaction solution returns to 25 DEG C, confirm the disappearance of di-t-butylchlorophosphine by gas-chromatography.Thereafter, in reaction solution, add 3% aqueous sulfuric acid 8ml carry out separatory, then wash organic layer.Then add 10% aqueous sulfuric acid 56ml to stir after 30 minutes and carry out separatory.After lower floor is cleaned with toluene 6ml, add hexane 29ml and 20% caustic soda aqueous solution 20ml and stir and carry out separatory in 30 minutes.After being washed on upper strata, add the methanol solution 45.9g (0.012mol) of palladium tetrachloride acid (II) sodium, reflux 10 minutes.Then, filter after being cooled to 25 DEG C, and clean with methyl alcohol 29ml.Obtained solid is carried out drying, thus obtains as yellow solid two (di-t-butyl prenyl phosphine) the palladium chloride 6.1g (yield 41%) becoming target.
1H-NMR collection of illustrative plates (CDCl 3) δ ppm:1.47 (d, J=6.8Hz, 9H, (C h 3 c) 2-P-), 1.49 (d, J=6.8Hz, 9H, (C h 3 c) 2-P-), 1.63 (s, 3H ,-CH=CC h 3 (CH 3)), 1.74 (s, 3H ,-CH=CCH 3(C h 3 )), 2.82 (br-s, 2H, (CH 3c) 2p-C h 2 -), 5.57 (br-s, 1H ,-C h=C (CH 3) 2) molten point 213 DEG C (decomposition)
[embodiment 6]
The manufacture of two (dicyclohexyl prenyl phosphine) palladium chloride
Dicyclohexyl phosphonium chloride is used to replace di-t-butylchlorophosphine, in addition, react by method similarly to Example 5, result obtains as yellow solid two (dicyclohexyl prenyl phosphine) the palladium chloride 7.5g (yield 44%) becoming target.
1H-NMR collection of illustrative plates (CDCl 3) δ ppm:1.14-1.32 (m, 6H), 1.57-1.72 (m, 6H), 1.67 (s, 3H ,-CH 2cH=C (C h 3 ) 2), 1.72 (s, 3H ,-CH 2cH=C (C h 3 ) 2), 1.79-1.84 (m, 6H), 2.04 (br-d, 12.4Hz), 2.15 (m, 2H), 2.79 (br-s, 2H, P-C h 2 -CH=C (CH 3) 2), 5.33 (br-s, 1H ,-C h=C (CH 3) 2) molten point 193 DEG C (decomposition)
[comparative example 1]
The synthesis of '-diphenyl-phenylene-diamine and chloro-1, the 3-dimethylbenzene of 2-carry out N, N '-bis-(1,3-xylyl)-N, N '-phenylbenzene-Isosorbide-5-Nitrae-phenylenediamine by N, N
Under non-active gas atmosphere, by N, N '-diphenyl-phenylene-diamine (10mmol), 2-chloro-1,3-dimethylbenzene (22mmol), acid chloride (0.1mmol), di-tert-butyl-phenyl phosphine (0.2mmol), sodium tert-butoxide (30mmol) and o-Xylol (40mL) carry out stirring for 6 hours in 130 ~ 135 DEG C, and use internal standard substance matter to be undertaken quantitatively by HPLC obtained reaction mixture, result obtains with yield 46% N becoming target, N '-bis-(1,3-xylyl)-N, N '-phenylbenzene-Isosorbide-5-Nitrae-phenylenediamine.(test again of patent documentation 2)
[embodiment 7]
Two (di-t-butyl crot(on)yl phosphine) palladium chloride (0.1mmol) is used to replace di-tert-butyl-phenyl phosphine and acid chloride, in addition, react under the condition identical with comparative example 1, result becomes the N of target, N '-bis-(1,3-xylyl)-N, N ' yield of-phenylbenzene-Isosorbide-5-Nitrae-phenylenediamine is 82%.Like this, manufacture method of the present invention can obtain target compound with high yield compared with the manufacture method of comparative example 1 (test again of patent documentation 2).
[comparative example 2]
2,6-dimethyl-N is carried out, the synthesis of N-phenylbenzene aniline by N, N-pentanoic and chloro-1, the 3-dimethylbenzene of 2-
Under non-active gas atmosphere, by N, N-pentanoic (2.0mmol), 2-chloro-1,3-dimethylbenzene (3.0mmol), two (di-t-butyl allyl group phosphine) palladium chloride (0.01mmol), sodium tert-butoxide (3.6mmol) and o-Xylol (4mL) carry out stirring for 6 hours in 145 DEG C, and use internal standard substance matter to be undertaken quantitatively by HPLC obtained reaction mixture, result obtains become target 2 with yield 29%, 6-dimethyl-N, N-phenylbenzene aniline.
[embodiment 8]
Two (di-t-butyl prenyl phosphine) palladium chloride (0.01mmol) is used to replace two (di-t-butyl allyl group phosphine) palladium chloride, in addition, react under the condition identical with comparative example 2, result is become target 2,6-dimethyl-N, the yield of N-phenylbenzene aniline is 68%.Like this, manufacture method of the present invention can obtain target compound with high yield compared with the manufacture method of comparative example 2.
[comparative example 3]
The synthesis of (N-chloro-phenyl-)-2，4，6-trimethyl aniline is carried out by 2，4，6-trimethyl aniline and the bromo-2-chlorobenzene of 1-
Under non-active gas atmosphere, by 2,4,6-trimethylaniline (10.0mmol), 1-bromo-2-chlorobenzene (10.0mmol), two (tri-butyl phosphine) palladium (0.01mmol), sodium tert-butoxide (12.0mmol) and o-Xylol (20mL) carry out stirring for 6 hours in 140 DEG C.The result that the GC of reaction mixture analyzes is obtain with yield 31% (N-the chloro-phenyl-)-2，4，6-trimethyl aniline becoming target.
[comparative example 4]
Use Palladous chloride (0.01mmol), di-t-butyl (4-dimethylaminophenyl) phosphine (0.02mmol) replace two (tri-butyl phosphine) palladium, in addition, react under the condition identical with comparative example 3, result becomes (the N-chloro-phenyl-)-2 of target, the yield of 4,6-trimethylaniline is 70%.
[embodiment 9]
Two (di-t-butyl crot(on)yl phosphine) palladium chloride (0.01mmol) is used to replace two (tri-butyl phosphine) palladium, in addition, react under the condition identical with comparative example 3, result is (the N-chloro-phenyl-)-2 becoming target, the yield of 4,6-trimethylaniline is 94%.Like this, target compound can be obtained with high yield compared with the manufacture method of manufacture method of the present invention and comparative example 3 and comparative example 4.
[comparative example 5]
The synthesis of 2,4 ', 6-trimethylbiphenyl is carried out by chloro-1, the 3-dimethylbenzene of 2-and 4-methylphenylboronic acid acid anhydride
Under non-active gas atmosphere, by chloro-for 2-1,3-dimethylbenzene (10mmol), 4-methylphenylboronic acid acid anhydride (5mmol), Palladous chloride (0.1mmol), di-t-butyl (4-dimethylaminophenyl) phosphine (0.2mmol), salt of wormwood (20mmol), Isosorbide-5-Nitrae-dioxan (27mL) and water (3mL) carry out stirring for 5 hours in 80 DEG C.The result that the GC of reaction mixture analyzes is obtain become target 2,4 ', 6-trimethylbiphenyl with yield 84%.(test again of non-patent literature 1)
[comparative example 6]
Two (tri-butyl phosphine) palladium (0.1mmol) is used to replace di-t-butyl (4-dimethylaminophenyl) phosphine and Palladous chloride, in addition, react under the condition identical with comparative example 5, result is become target 2, the yield of 4 ', 6-trimethylbiphenyl is 60%.
[embodiment 10]
Two (di-t-butyl crot(on)yl phosphine) palladium chloride (0.1mmol) is used to replace di-t-butyl (4-dimethylaminophenyl) phosphine and Palladous chloride, reaction times is 3 hours, in addition, react under the condition identical with comparative example 5, result is become target 2, the yield of 4 ', 6-trimethylbiphenyl is 91%.Like this, compared with the manufacture method of manufacture method of the present invention and comparative example 5 (test again of non-patent literature 1) and comparative example 6, can also Reaction time shorten, thus target compound can be obtained with high yield.
[embodiment 11]
Using di-t-butyl crotons Ji Phosphonium a tetrafluoro borate (0.20mmol), two (bis-Ya Benzyl benzylacetone) palladium (0.10mmol) replaces two (di-t-butyl crot(on)yl phosphine) palladium chloride, in addition, react under the condition identical with comparative example 5, result is the 2-methoxyl group-4 becoming target ' yield of-methyl diphenyl is 92%.
[comparative example 7]
2-methoxyl group-4 is carried out by 2-chloroneb and 4-methylphenylboronic acid acid anhydride ' synthesis of-methyl diphenyl
Under non-active gas atmosphere, 2-chloroneb (10mmol), 4-methylphenylboronic acid acid anhydride (7mmol), two (tri-butyl phosphine) palladium (0.05mmol), potassiumphosphate (15mmol), Isosorbide-5-Nitrae-dioxan (18mL) and water (2mL) are carried out stirring for 2 hours in 100 DEG C.The result that the GC of reaction mixture analyzes is obtain with yield 72% the 2-methoxyl group-4 becoming target '-methyl diphenyl.
[comparative example 8]
Use Palladous chloride (0.05mmol), di-t-butyl (4-dimethylaminophenyl) phosphine (0.1mmol) replace two (tri-butyl phosphine) palladium, in addition, react under the condition identical with comparative example 7, result is the 2-methoxyl group-4 becoming target ' yield of-methyl diphenyl is 78%.
[comparative example 9]
Use palladium (0.05mmol), di-t-butyl-normal-butyl phosphine (0.10mmol) replace two (tri-butyl phosphine) palladium, in addition, react under the condition identical with comparative example 7, result is the 2-methoxyl group-4 becoming target ' yield of-methyl diphenyl is 75%.
[embodiment 12]
Two (di-t-butyl prenyl phosphine) palladium chloride (0.05mmol) is used to replace two (tri-butyl phosphine) palladium, in addition, react under the condition identical with comparative example 7, result is the 2-methoxyl group-4 becoming target ' yield of-methyl diphenyl is 93%.Like this, manufacture method of the present invention can obtain target compound with high yield compared with the manufacture method of comparative example 7 ~ 9.
[comparative example 10]
The synthesis of 2-ethenylmethoxy benzene is carried out by 2-bromobenzene ether and vinyl boronic acids acid anhydride-pyridine complex
Under non-active gas atmosphere, 2-bromobenzene ether (10mmol), vinyl boronic acids acid anhydride-pyridine complex (4mmol), two (tri-butyl phosphine) palladium (0.05mmol), potassiumphosphate (15mmol), Isosorbide-5-Nitrae-dioxan (18mL) and water (2mL) are carried out stirring for 6 hours in 80 DEG C.The result that the GC of reaction mixture analyzes is obtain with yield 54% the 2-ethenylmethoxy benzene becoming target.
[embodiment 13]
Two (di-t-butyl crot(on)yl phosphine) palladium chloride (0.05mmol) is used to replace two (tri-butyl phosphine) palladium, in addition, react under the condition identical with comparative example 10, result is the yield of the 2-ethenylmethoxy benzene becoming target is 87%.Like this, manufacture method of the present invention can obtain target compound with high yield compared with the manufacture method of comparative example 10.
[comparative example 11]
The synthesis of 9-(3-chloro-phenyl-)-9H-carbazole is carried out by the bromo-3-chlorobenzene of 1-and carbazole
Under non-active gas atmosphere, carbazole (10mmol), 1-bromo-3-chlorobenzene (11mmol), two (di-tert-butyl-phenyl phosphine) palladium chloride (0.3mmol), sodium tert-butoxide (15mmol) and o-Xylol (80mL) are carried out stirring for 9 hours in 135 DEG C, use internal standard substance matter to be undertaken quantitatively by GC obtained reaction mixture, result obtains with yield 67% 9-(3-the chloro-phenyl-)-9H-carbazole becoming target.
[embodiment 14]
Two (di-t-butyl crot(on)yl phosphine) palladium chloride (0.3mmol) is used to replace two (di-tert-butyl-phenyl phosphine) palladium chloride, in addition, react under the condition identical with comparative example 11, result is the yield of 9-(3-the chloro-phenyl-)-9H-carbazole becoming target is 95%.Like this, manufacture method of the present invention can obtain target compound with high yield compared with the manufacture method of comparative example 11.
[embodiment 15]
The synthesis of 4-tolyl morpholine is carried out by 2-toluene(mono)chloride and morpholine
Under non-active gas atmosphere, 2-toluene(mono)chloride (10mmol), morpholine (12mmol), two (di-t-butyl crot(on)yl phosphine) palladium chloride (0.01mmol), sodium tert-butoxide (12mmol) and o-Xylol (20mL) are carried out stirring for 6 hours in 135 DEG C, the result that the GC of the reaction mixture obtained analyzes is obtain with yield 58% the 4-tolyl morpholine becoming target.
[embodiment 16]
The synthesis of 4 '-methyl biphenyl-4-formonitrile HCN is carried out by 4-6-chlorophenyl nitrile and 4-methylphenylboronic acid acid anhydride
Under non-active gas atmosphere, by 4-6-chlorophenyl nitrile (10mmol), 4-methylphenylboronic acid acid anhydride (7mmol), two (1,5-cyclooctadiene) nickel (0.5mmol), di-t-butyl crot(on)yl phosphine (1.0mmol), potassiumphosphate (15mmol), Isosorbide-5-Nitrae-dioxan (18mL) and water (2mL) in 80 DEG C carry out 6 hours stir.The result that the GC of reaction mixture analyzes is obtain with yield 88% the 4 '-methyl biphenyl-4-formonitrile HCN becoming target.

Claims (16)

1. a phosphine compound, is characterized in that, is represented by following general formula (1),
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
2. phosphine compound according to claim 1, is characterized in that, R in general formula (1) 1with R 2be the tertiary butyl.
3. phosphine compound according to claim 2, is characterized in that, is represented by following formula (2)
。
4. phosphine compound according to claim 2, is characterized in that, is represented by following formula (3)
5. a coordination compound catalyzer, is characterized in that, the phosphine compound that following general formula (1) represents be coordinated in be selected from the periodic table of elements the 8th race, the 9th race, the 10th race and the 11st race transition metal and formed,
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
6. coordination compound catalyzer according to claim 5, it is characterized in that, transition metal is selected from Pd, Ni, Pt, Rh, Ir, Ru, Co, Fe, Cu and Au.
7. coordination compound catalyzer according to claim 6, is characterized in that, is represented by following formula (4),
PdCl 2(tBu 2P-CH 2-CH＝CH-CH 3) 2(4)
In formula, tBu represents the tertiary butyl.
8. coordination compound catalyzer according to claim 6, is characterized in that, represented by following formula (5).
PdCl 2(tBu 2P-CH 2-CH＝C(CH 3) 2) 2(5)
9. Yi Zhong phosphonium salt compound, is characterized in that, is represented by following general formula (6),
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, Y -represent B -f 4or B -ph 4, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
10. according to claim 9 Suo Shu phosphonium salt compound, it is characterized in that, R in formula (6) 1and R 2for the tertiary butyl.
The manufacture method of 11. 1 kinds of aromatics, it is characterized in that, the phosphine compound that formula (1) is represented and/or formula (6) Biao Shi phosphonium salt compound be selected from the 8th race of the periodic table of elements, the 9th race, the 10th race and the 11st race transistion metal compound add in reaction solution and generate coordination compound, using this coordination compound as catalyzer or as catalyst system at least partially, and use this catalyzer or catalyst system
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4be asynchronously hydrogen atom,
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, Y -represent B -f 4or B -ph 4, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
The manufacture method of 12. 1 kinds of aromatics, it is characterized in that, the phosphine compound that following general formula (1) represents be coordinated in be selected from the periodic table of elements the 8th race, the 9th race, the 10th race and the 11st race transition metal thus form coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
The manufacture method of 13. 1 kinds of aromatic amines compounds, it is characterized in that, comprise following content: the phosphine compound that formula (1) is represented and/or formula (6) Biao Shi phosphonium salt compound be selected from the 8th race of the periodic table of elements, the 9th race, the 10th race and the 11st race transistion metal compound add in reaction solution and generate coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system, make to have the aromatics of halogen atom and/or reactive behavior base and primary amine and/or secondary amine to react
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4be asynchronously hydrogen atom,
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, Y -represent B -f 4or B -ph 4, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
The manufacture method of 14. 1 kinds of aromatic amines compounds, it is characterized in that, comprise following content: the phosphine compound that following general formula (1) represents be coordinated in be selected from the periodic table of elements the 8th race, the 9th race, the 10th race and the 11st race transition metal thus form coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system, make to have the aromatics of halogen atom and/or reactive behavior base and primary amine and/or secondary amine to react
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
The manufacture method of 15. 1 kinds of aromatics, it is characterized in that, comprise following content: the phosphine compound that formula (1) is represented and/or formula (6) Biao Shi phosphonium salt compound be selected from the 8th race of the periodic table of elements, the 9th race, the 10th race and the 11st race transistion metal compound add in reaction solution and generate coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system, the aromatics and the boron compound that make to have halogen atom and/or reactive behavior base react
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4be asynchronously hydrogen atom,
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, Y -represent B -f 4or B -ph 4, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
The manufacture method of 16. 1 kinds of aromatics, it is characterized in that, comprise following content: the phosphine compound that following general formula (1) represents be coordinated in be selected from the periodic table of elements the 8th race, the 9th race, the 10th race and the 11st race transition metal thus form coordination compound, using this coordination compound as catalyzer or using at least partially as catalyst system, the aromatics and the boron compound that make to have halogen atom and/or reactive behavior base react
In formula, R 1and R 2represent secondary alkyl, tertiary alkyl or cycloalkyl independently of one another, R 3and R 4represent hydrogen atom, fatty group, assorted fatty group, aromatic series base, ester ring type base or hetero ring type base independently of one another, in addition, R 3and R 4not there is phosphorus atom, in addition, R 3and R 4it is asynchronously hydrogen atom.
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